Polyalkylene polyamines



United States Patent 2,767,21 i POLYALKYLENE POLYAMINES Frederick C. Bersworth, Framingham Center, Ma ss., as-

signor to The Dow Chemical Company, Midland, Mich, a corporation of Delaware No Drawing. Application June 3, 1952, Serial No. 291,577

6 Claims. (Cl. 260-584) This invention relates to chemical compounds and more particularly to organic chemical compounds and has for its object the provision of a new type of polyalkylene polyamines having nitrogen atoms in the end amino group thereof which are capable of reacting chemically independently of the other and interior nitrogen atoms in the molecule.

Another object is to provide poly hydroxy polyalkylene polyamines conforming to the general structural formula:

wherein Y is a bivalent alkylene chain containing from 2 to 3 carbon atoms; X is a bivalent alkylene radical of from 4 to 12 carbon atoms which may be interrupted with ether oxygen atoms; Z is a bivalent alkylene radical of from 2 to 6 carbon atoms which may be either branched or straight chained; and A is a member of the group consisting of hydrogen and one of the substituent groups consisting of methyl, ethyl, n-propyl, isopropyl and butyl.

Still another object is to provide polyhydroxy polyalkylene polyamines having end amino groups therein containing an amino nitrogen which is capable of independent chemical reaction as a tertiary nitrogen, thereby adapting the polyamine for wide utility as an intermediate in the formation of a large number of amino compounds of great utility in the art.

Other objects will be apparent as the invention is more fully hereinafter disclosed.

In accordance with these objects I have discovered that the polyhydroxy polyalkylene polyamines conforming to the above formula are of great utility in organic synthesis reactions due to the fact that the X groups present therein space the end amino groups away from the interior nitrogens sutficiently to permit these end nitrogens to react chemically as a tertiary nitrogen independently of the interior spaced nitrogen's, thus permitting the compound to act chemically in the formation of a large number of chemical compounds,,based on this reaction and on the substitution of one or both of the remaining hydrogens on the interior amino nitrogens.

For the purpose of this invention certain limitations are put upon the various alternatives for X, Y, Z and A in the compound. Bearing in mind that the preferred compounds are designed to contain end amino groups containing nitrogen atoms reactive as tertiary nitrogens independently of the interior nitrogen atoms, thereby adapting the compound to function as intermediates in further syntheses, these limitations are of the essence of the invention.

In order to permit the nitrogen atoms of the end compound must contain at least four carbon atoms and up to 12 carbon atoms. Adequate solubility of the com- 2,767,214 Patented Oct. 16, 1956 pounds in water is a desirable but not a necessary requisite for these compounds, and other" factors being equal,.I have discovered that with increase in the size and weight of the various radicals X, Y, ZandA, the water solubility of the polyalkylol polyalkylene polyamine compounds decreases and their solubility in organic solvents increases. If X represents an alkylene group which contains an ether oxygen linkage, a greater size and weight of the X radicals can be tolerated in the water soluble compounds befoie solubility decreases because of the enhanced solubilizing effect of the oxygen atom.

The compounds of this invention are produced by initially reacting two molecular proportions of the ap propriate halogen substituted alkyl or alkoxyalkyl dialkanolamine, for example, 2-chloroethoxy-ethyldiethanolamine, with one molecular proportion of the appropriate alkylene diamine, such as, ethylene diamine, under conditions such as to insure a substantial yield of the polyalkylol polyalkylene polyamine derivative.

Another method which may be employed to produce the compounds of this invention consists in reacting the proper symmetrical chloroalkyl or chloroalkoxyalkyl ethylene diamine, such as N,N'-di-(4-chlorobutyl)-ethylene diamine, under suitable conditions with the appropriate dialkanolamine, for example, diethanolamine, in a one to two molar ratio.

Although these compounds can be prepared by methods other than those described above and also by modifications which will appear to those skilled in the art, I prefer to use the procedure followed in the specific examples hereinafter given since it is easily carried out, requires the use of simple and uncomplicated apparatus and involves a minimum of manipulation.

It has been found that in general the longer the bivalent alkylene group in the X positions, the moreindependent the alkylol substituted nitrogen atoms in the end amino groups become in their chemical reactions. The so constructed polyfunctional nitrogen compounds permit the production of thus far unobtainable quaternary type compounds and compositions of matter, such as soaplike amino products which are highly useful in industry.

This invention will be further illustrated by the following examples. It should be understood that although these examples may describe some specific manipulative steps in detail which may be employed in the preparation of these compounds, they are given primarily by way of illustration and not by way of limitation and the invention in its broader aspects is not to be restricted to these examples.

Example I alcohol containing two mols of sodium hydroxide as acid 55 acceptor. The mixture was heated to reflux for an additional 4 hours. The sodium bromide present in the reaction solution was removed by filtration and the alcohol content of the reaction solution was removed by distillation at atmospheric pressure. The product obtained was a viscid yellow liquid soluble in water, alcohols and somewhat soluble in acetone. Chemical analysis of this compound confirmed that the compound may be representedby the following formula:

.diethyl ethylene diaminein 500 ml. of isopropyl alcohol containing two'rnols of sodium hydroxide there was gradually added over a period of four hours, two mols of tent was-distilled (SE. The pale yellow viscous residue of omega chloro dodecyl diethanolamine. The mixture was compounds may be employed: alkylene diamines, halogen th n held at gentle reflux for an ddi qa l 191 HPi E E5 l sxl a d. qx -al d a k na ami e sym- Th' sodium chloride content of the reaction solution was metrical chloro alk yl 53d chlofoalkoxyalkyl alkylene di- 7 removed by filtration and the isopropyl alcohol content amines and dialkanolamines.

of the reaction solution was distilled oijf. The resulting 5 Alkylene diarnines suitable for making the new comproduct, N,N"-di{(omega-iininodiethanol-dodecyl) -N,N pounds in accordance with the above specific examples, diethyl ethylene 'diaini'ne' is a viscousiyellow liquid soluble include the following: ethylene diamine, isopropylene diin water'and "manners and chemical analysis confirmed amine, trimethylene diamine,N,N-dimethyl-ethylene dithe'fact that'the compound has thebformul a: amine, N,N"-diethyl isopropylene diamine, N,N'-diethyl oom-om 02m 5 01m, one-onion th d a' N, '-d -P 9P )'f y fi T E WH butyl ethylene diamine.

HOCHz-O 1 7 032 1193 The following halogen substituted alkyl and alkoxyalkyl I I Ex 1H dialkanolamines also "may be employed as starting mate- TO a gently fl i Solution Oftwo l f dib t L rials to react with theahove alkylene diamines to make amine in 500 ml. of isopropyl alcohol containing two the new 11 hi llY l i ll N'i mols of sodium hydroxide, there was slowly added one y diethalllamifle, p y diethanolp1; g I LNQdi (z ht th th l)- fl l di mjn amine, N-(6-chlorohexyl)-d1ethanolam1ne, N-(8-chloroover affou'r hour period. The mixture was gently Ieqty l-g i t an m pe, 7? 9 9 9 9 'd P PQQ fluxed for an additional four hours after which the sodium amine, N-( l c hlorobutyl)-dipropanolarnine, N-(12-chlochloride content of the reaction solution was filtered off dP QQY hfi l l q n N-(Q-C QIQhQXyD dibutanoland the isopropyl alcohol content thereof was removed afnlng and N -(fl -chlorobutyl)-di1sopropanolamine. by distillation. Suitable symmetrical chloroalkyl or chloroalkoxyalkyl The product, N,N-di-(2-iminodibutanol-ethoxyethy1)- allgylene diamines in the production of the compounds of ethylene diamine is a viscid yellow liquid soluble in water 29 the present invention consist of: N,N'-di-(4-chlorobutyl)- and alcohols and was found to have the formula: ethylene diamine, N,N di-(2;chloroethoxyethyl)-ethylene ladom n 7 a p onahon N-Q H CHQO-CH -CH -N-CHq-OH -N-OHfiCHpO-OHz-C H N Ho(oH,)r V can on.

Example IV diamine, N,N..- di-(6-chloro-hexyl)-ethylene diamine, N,-

N'di-(l2-chlorododecyl)-ethylene diamine, N,N'-di-(2- chloroethoxyethyl) trirnethylene diamine, N,N'-di-(4- chlor bu tylY-trifmethylene diamine, N,N'-di-(4-chlorobutylj-isopropylene diamine, N,N'-di-(2-chloroethoxy- 0.5 mol of N-(4-chlorobutyl)-dipropanolamine was gradually added over a period of two hours to a slowly re fiuxing solution of 0.25 mol of N,N-diethyl trimethylene' diamine in 500 ml. of isopropyl alcohol containing 0.5 mol of sodium hydroxide. The mixture was held at gentle reflux for an additional six hours after which time it-was cooled, the sodium chloride content of the solution was removed by'filtration and the isopropyl: alcohol con- N'-dimethyl ethylene diamine, N ,N'-di-(2-chloroethoxychloroethoxyethyl) N,I{'-dibutyl ethylene diamine, and

p p y ,N'- iethyl -trimeth NN- i-WW IO DrlE h methylene ylene diamine is soluble in water'and alcohols and was 9 -Fq P f m m compounds also may f und to havthe f m llaf Y I be employed ethyl)-isopropylene diamine, N,N'-di-( 4-chlorobutyl) -N,-'

'Thedialkanolamine radicals present in the compounds QQH Js 02 s 0135, (CH P-0E of this invention may be selected from a relatively large N(CHz)4-NCHg-CHz-CHr-N-(CHflA-N classjfor example, diethanolamine, diisopropanolamine,

' (GH2)a OH di-n-propanolamine, di-n-butanolamine, 'di-iso-butanol- 7 amine, dipentanolamme and dihexanolamlne.

. ml V In addition to the compounds'described above, 1,2-di- To a gently refluxing solution of 0.2 mol of dimethyl aminociyclohexane or its N,N-di-chloroall yl' derivatives ethylene diamine in 300 ml. of isopropyl alcohol conmay' be used; A preferred compound of this series is protaining 0.4'mol of sodium hydroxide there was added duced-fro'm 1,2-diaminocyclohexane and N-(Z-chlorodropwise over a three-hour period, 0.4 mol of N-(Z-chloroethoxyethyl)-diethanolamine and is represented by the ethoxyethyl)-diethanolamine' 'Ihemixturewasgentlyrefollowing'form'ula:

r l lye-om H2 0\ .H2. CH i'jGHflOH HC-VO-H V CHr-CHzOH N z CHr0 CEtCHr l i-on om-o-om on rr ,Hr-OHrO 11 H, orb-onion fluxed for an additional four hours after which the sodium The above starting materials are mentioned only for chloride content of the reaction solution was removed by purposes of illustration and not for limitation of the infiltration and the isopropyl alcohol content thereof .was vention. Obviously other members of the classes indiremoved bydistillation. The viscous yellow reaction prodcatect by the definitions previously given for the radicals not, N,N-di-(Z-iminodiethanol ethoxyethyl') -N,N'-'- di X, Y, Z andA can be employed in the production of the methyl-ethylene diamine, is soluble in water andalcohols polyhydroxy polyalkylene'polyamines of the present inand was found to have'th e formula: venti ?H2CH2OH ou 2 1 ing-onion N -CH aQHz0OHr-CH2-N-OHz GHr-NC:QE::QCH QH N neomorr our-onion.

From the above specific examples of compounds fall- Thecompoundsof thisinventionpossess interesting and ing: within the broad scope of the present invention, it"is useful propertiesas surfiace active agents, detergents,

' believed apparent that as starting materials thefollowing wetting ;ag ents 'arid as intermediates-inthe production of thus far unobtainable compounds and have, therefore, wherein Y is an alkylene radical containing 2-3 carbon diverse applications. They may, for example, serve as atoms; X is selected from the group consisting of alkyl-ene intermediates in the producti..n :of soap-like amino comradicals having 412 carbon atoms in the chain such that pounds having the generic formula: the indicated nitrogen atoms are separated by 'at least 4 5 carbon atoms, and the ethoxy ethyl radical; Z is an ailkylene radical having 2-6 carbon atoms; and A is I selected from the group consisting of hydrogen, methyl, HOZ I A A Z0H ethyl, n-propyl, isopropyl and bu-tyl radicals.

Fatty Fatty 2. The compound N,N' di-(4-i-minodiethanol-butyl)- Acid Acid isopr-opylene diamine conforming to the following which in some respects are similar to the allsan-olamiue formula: soaps. These soap-like amino products are readily HO CHz-CH: H CH H GHQ-CHQQH formed by adding a fatty acid to an aqueous solution of l i the polyalkylol polya'lkylen-e polyamme 111 the FEIPPIOXI- mate molar ratios above indicated and heating the miX- HO CHrc CHTCHZOH ture to complete the formation of the soap-like amino 3- The compound N,N di-(omega-iminodiethanolproduct. These soap-like amino products are soluble in y diefllyl ethylene? diamine having me water and to some extent are also soluble in solvents. fo 'flr The compounds of the present invention also are espe- 30032.03, 62H5 H2011 cially useful as intermediates for the production of surface-active agents and as additives to lubricants and N (CH2) N CHTCHR N (CH)lrN .grwe HO CHz-CHz CHrCHgOH The soap-like amino compounds above described offer 4. The compound N,N-di-(2-iminodibutanol-ethoxywide utility in the an as assistants in textile and leather ethyD-ethylene diamine conforming to the following manufacture, in glass and metal cleaners, dry cleaners, formula:

lubricants, soap compositions and in numerous miscel- 5. The compound N,N-di-(imino dipropanol-butyl) l-aneous applications where detergency and wetting action N,N'diethyl-trimethylene diamine conforming to the folure desired in combination. lowing formula:

Having hereinabove disclosed the present invention How]; 0 H Cm CH generically and specifically and having given a plurality 2 5 2 of specific examples thereof, it is believed apparent that N (CH) N CH CH2CHTN(CH)"N the compounds of the invention may be widely varied HOWHQS CHM-0H without essential departure therefrom and all such modi- 6. The compound N,N'-di-(2-imino diethanol-ethoxyfications and adaptations thereof are contemplated as ethyl)-N,N' 'dimethyl-ethylene diamine conforming to the may fall within the scope of the following claims. following formula:

cm-cmofi 3H, (3H: cm-omon N-CHg-CH -O-CHg-CH -N-CH -CH -NCH CHr-OCH;CH:N

Hr-CHgOH Hg-CHgOH f f gfig ggg es ondin to the amt a1 References Cited in the file of this patent fonhula p g g UNITED STATES PATENTS Hoz ZOE 2,243,329 De Groote et a1. May 27, 1941 N/ 2,248,729 Ulrich et a1 July 8, 1941 N X N'Y N X 5o OREIGN PA HOZ/ i L ZOH F TENTS 364,104 Great Britain Dec. 28, 1931 

1. CHEMICAL COMPOUNDS CORRESPONDING TO THE GENERAL FORMULA 